JP2023078312A - Moisture-curable polyolefin formulation - Google Patents

Abstract

To provide a moisture-curable polyolefin formulation which enhances condensation of moisture-curable polyolefins and comprises environmentally safe, non-toxic catalysts.SOLUTION: There is provided a moisture-curable polyolefin formulation comprising a (hydrolyzable silyl group)-functional polyolefin prepolymer and a condensation-cure catalyst system comprising and/or made from a mixture of a compound that is a carboxamidine or a guanidine and a compound that is a cobalt acetylacetonate or a zinc acetylacetonate, wherein each compound independently is unsubstituted or substituted. There are also provided methods of making and using the same, a cured polyolefin made therefrom, and articles containing or made from the same, and condensation-cure catalyst systems useful therein.SELECTED DRAWING: None

Description

Moisture Curable Polyolefin Blends and Related Aspects.

INTRODUCTION Patent application publications and patents in or relating to this field are US 2009/0156
737 (A1), US2011/0046304 (A1), US2011/009842
0 (A1), US2014/0329090 (A1), US2016/0319081 (
A1), US2018/0244828 (A1), US4293597, US44618
67, US5945466, US5985991, US7365145, US74857
29 (B2), US7527838 (B2), US8877885 (B2), US900
6357 (B2), US9175188 (B2), US9328205 (B2), and US9976028 (B2).

We have discovered that curing catalyst systems based on certain transition metal acetylacetonate compounds enhance the condensation of moisture-curable polyolefins and are therefore useful as environmentally safe, non-toxic catalysts. Our technical solution comprises a (hydrolyzable silyl group)-functional polyolefin prepolymer and a mixture of a compound that is carboxamidine or guanidine and a compound that is cobalt acetylacetonate or zinc acetylacetonate and/or and a condensation cure catalyst system made therefrom, each compound independently comprising a moisture-curable polyolefin formulation that is unsubstituted or substituted. Also included are methods of making and using the same, cured polyolefins made therefrom, and articles containing or made therefrom. Also included are condensation cure catalyst systems useful therein.

The synopsis and abstract are incorporated herein by reference. Embodiments include the following numbered aspects and detailed description, including examples.

Aspect 1. A moisture-curable polyolefin formulation comprising (A) (hydrolyzable silyl groups)
- a functional polyolefin prepolymer and (B) a carboxamidine or guanidine, unsubstituted or substituted compound (collectively referred to as "(aza)carboxamidine") with a cobalt acetylacetonate coordination complex or zinc Compounds that are acetylacetonate coordination complexes, wherein each acetylacetonate is independently unsubstituted ("aca
(abbreviated as "alkyl-acac"), or substituted with 1 to 5 alkyl groups (abbreviated as "alkyl-acac"), each alkyl group being unsubstituted ("Co, Zn(alkyl)acetylaceto and a condensation curing catalyst system comprising a mixture made by contacting the Co,Zn(alkyl)acetylacetonate with cobalt. (II) ((alkyl)acetylacetonate) ₂
(abbreviated as Co(II)((alkyl)acac) ₂ ), cobalt(III)((alkyl)acetylacetonate) ₃ (abbreviated as Co(III)((alkyl)acac) ₃ ), and Zinc(II) ((alkyl)acetylacetonate) ₂ (Zn(II)
(abbreviated as (alkyl)acac) ₂ ), respectively, the amount of (A) is 79.0 to 99.99 percent by weight (wt.%)
and the amount of (B) is 21.0 to 0.01% by weight, and (B) the condensation curing catalyst system is 1
A moisture-curable polyolefin formulation characterized by a (aza)carboxamidine/Co,Zn(alkyl)acetylacetonate molar ratio of 5:0.15. , carboxamidine can be a compound of formula (I) as described below. Guanidine can be a compound of formula (II) described below. Co,Zn(alkyl)acetylacetonate is Co(II)((alkyl)a
from cac) ₂ and Co(III)((alkyl)acac) ₃ , or from Co(II
)((alkyl)acac) ₂ and Zn(II)((alkyl)acac) ₂ , or from Co(III)((alkyl)acac) ₃ and Zn(II)((alkyl)a
from cac) ₂ , or from Co(II)((alkyl)acac) ₂ , or from Co
(III) from ((alkyl)acac) ₃ or Zn(II)((alkyl)ac
ac) can be selected from ₂ ; A moisture-curable polyolefin formulation may consist of (A) and (B) only. Alternatively, the moisture-curable polyolefin formulation may comprise (A), (B), and at least one of (A), (B), (aza)carboxamidine, or Co,Zn(alkyl)acetylacetonate. and the amount of (A) can be from 79.1 to 99.89% by weight and the amount of (B) is 0.01%, all based on the total weight of the moisture-curable polyolefin formulation. ~20.8 wt% and the total amount of at least one additive can be from 0.10 to 20.89 wt%. Examples of optional additives and amounts thereof are described below.

Aspect 2. (A) (Hydrolyzable silyl group)-functional polyolefin prepolymer has the following limitations (i)-(iii): (i) each hydrolyzable silyl group independently has the formula (R ² ) _m (R ³ )
_3-m Si—(II) monovalent group, wherein subscript m is an integer of 1, 2, or 3, and each R ² is independently H, HO—, ( C ₁ -C ₆ )alkoxy, (C ₂ -C ₆ )
carboxy, phenoxy, (C ₁ -C ₆ )alkyl)-phenoxy, ((C ₁ -C ₆ )alkyl) ₂ N-, (C ₁ -C ₆ )alkyl (H)C=NO-, or ((C ₁ -C ₆ )alkyl) ₂ C=NO- and each R ³ is independently (C ₁ -C ₆ )alkyl or phenyl, (ii) the polyolefin portion of (A) is polyethylene-based, polyethylene-
is a co-( _C3 - _C40 ) alpha-olefin) system, or a combination thereof; and (iii) both (i) and (ii). of moisture-curable polyolefin formulations. Each R ² may be free of H and HO—, or free of phenoxy and (C ₁ -C ₆ )alkyl-phenoxy.
Each R ² is independently (C ₁ -C ₆ )alkoxy, (C ₂ -C ₆ )carboxy, ((C ₁
—C ₆ )alkyl) ₂ N—, (C ₁ -C ₆ )alkyl(H)C═NO—, or ((C ₁
(C ₆ )alkyl) ₂ C=NO-; alternatively (C ₁ -C ₆ )alkoxy; alternatively (C ₂ -C ₆ ) carboxy; alternatively ((C ₁ -C ₆ )alkyl) ₂ N- alternatively (C ₁ -C ₆ )alkyl(H)C=NO-, alternatively ((C ₁ -C ₆ )alkyl) ₂ C
=NO-.

Aspect 3. (B) a mixture of condensation cure catalyst systems comprising (B1)-(B3): (B1) a blend of (aza)carboxamidine and Co,Zn(alkyl)acetylacetonate; (B2)
Reaction product (or reaction products) of reaction of (aza)carboxamidine with Co,Zn(alkyl)acetylacetonate; (B3) (B2) reaction product with (aza)carboxamidine and/or Co,Zn combination with (alkyl)acetylacetonate,
3. The moisture-curable polyolefin blend of aspect 1 or 2, which is any one of

Aspect 4. Each (alkyl)acetylacetonate of (alkyl)Co,Zn(alkyl)acetylacetonate is independently an unsubstituted acetylacetonate or (C ₁ -C ₆
) alkyl-substituted acetylacetonate, or unsubstituted acetylacetonate (ie, 2,4-pentanedionate), or (C ₁ -C ₆ ) alkyl-substituted acetylacetonate (ie, (C ₁ -C ₆ ) alkyl-substituted 2,4-pentanedionate),
The moisture-curable polyolefin formulation of any one of aspects 1-3. Each (C ₁ -C ₆ )alkyl-substituted acetylacetonate is independently 1 to 5 (C ₁ -C ₆ )alkyl groups, alternatively 1 to 4 (C ₁ -C ₆ )alkyl groups, alternatively 1 to 3 (C ₁ -C ₆ )alkyl groups, alternatively 2 to 5 (C ₁ -C ₆ )alkyl groups, alternatively 2 to 4 (C ₁ -C ₆ )
an alkyl group, or one (C ₁ -C ₆ )alkyl group, or two (C ₁ -C ₆ )
Having alkyl groups, each (C ₁ -C ₆ )alkyl group is unsubstituted and independently selected.
Unsubstituted acetylacetonates can be drawn as enolates of the formula H ₃ CC(=O)C(H)=C(O-)CH ₃ . Alternatively, at least one (alkyl)acetylacetonate, or all but one (alkyl)acetylacetonate, or each (alkyl)acetylacetonate may independently be an alkyl-substituted acetylacetonate, optionally The remaining (alkyl)acetylacetonates of may be unsubstituted. Alkyl-substituted acetylacetonates can be drawn as enolates of the formula R ^a ₃ CC(=O)C(R ^b )=C(O-)CR ^c ₃ , where at least one of R ^a -R ^c is unsubstituted ( C ₁ -C ₆ )alkyl and each of any remaining R ^a -R ^c is independently H or unsubstituted (C ₁ -C ₆ )alkyl. In some embodiments, at most two or only one of R ^a -R ^c are unsubstituted (C ₁ -C ₆ )alkyl, and each of any remaining R ^a -R ^c is is H. In some embodiments, each R ^a and R ^c is H and R ^b is unsubstituted (C ₁ -C ₆ )alkyl. In some aspects, all R ^a and R ^b and two R ^c are H;
One R ^c is unsubstituted (C ₁ -C ₆ )alkyl. In some aspects, unsubstituted (C ₁ -
_C6 )alkyl is methyl. In some aspects, each unsubstituted (C ₁ -C ₆ )alkyl is independently an unsubstituted (C ₁ -C ₃ )alkyl, or an unsubstituted (C ₄ -C ₆ )alkyl, or an unsubstituted ( C ₂ -C ₅ )alkyl, or methyl, or ethyl, or unsubstituted (C ₃ )alkyl group, or unsubstituted (C ₄ )alkyl group, or unsubstituted (C ₅
) alkyl group or an unsubstituted ( _C6 ) alkyl group. Examples of alkyl-substituted acetylacetonates are 3-methyl-acetylacetonate (R ^b is methyl and each R ^a and R ^c is H) and 1,1,5,5-tetramethyl-acetylacetonate (R ^b is H, 2 R ^a are methyl, 2 R ^c are methyl, the remaining R ^a and R
^c is H). Each (alkyl)acetylacetonate is independently an unsubstituted acetylacetonate or a methyl-substituted acetylacetonate, or 3-methyl-acetylacetonate or 1,1,5,5-tetramethyl-acetylacetonate Methyl-substituted acetylacetonate, or unsubstituted acetylacetonate.

Aspect 5. The moisture-curable polyolefin formulation of any of aspects 1-4, wherein the (aza)carboxamidine is an unsubstituted or substituted carboxamidine. The carboxamidine can be a compound of formula (I): R ² R ³ NC(=N-R ¹ )-C(R ⁴ ) ₃ (I), wherein R ¹ -R ⁴ are the limits ( r1) to (r4): (r1) each of R ¹ to R ⁴ is independently H or a (C ₁ -C ₄₅ ) hydrocarbyl group; (r2) any two of R ¹ to R ⁴ are joined together to form a (C ₁ -C ₄₅ )hydrocarbylene and the remaining R ¹ -R ⁴
is independently H or a (C ₁ -C ₄₅ ) hydrocarbyl group, (r3)R ¹
any three of ~R ⁴ are joined together to form a trivalent (C ₁ -C ₄₅ ) hydrocarbon triradical group and the remaining R ¹ -R ⁴ are H or (C ₁ -C ₄₅ ) hydrocarbyl and (r4) all of R ¹ -R ⁴ are joined together to form a tetravalent (C ₁ -C ₄₅ ) hydrocarbon tetraradical group is. Carboxamidines may be free of NH groups. When the (aza)carboxamidine is carboxamidine, the moisture-curable polyolefin formulation may be free of guanidine.

Aspect 6. carboxamidine is (i) to (xix): (i) 1,8-diazabicyclo [
5.4.0]undec-7-ene (“DBU”), (ii) 1,5-diazabicyclo[4
. 3.0] non-5-ene DBN, (iii) 1,2,4-triazole-1-carboximidamide, (iv) acetamidine, (v) aminoacetamidine, (vi) benzamidine, (vii) 4 -amino-benzamidine, (viii) 4-bromo-benzamidine, (ix) 4-chlorobenzamidine, (x) 4-fluorobenzamidine, (xi
) 4-hydroxybenzamidine, (xii) 4-methoxybenzamidine, (xii)
i) 4-methylbenzamidine, (xiv) 4-trifluoromethylbenzamidine, (
xv) N,N'-formamidine, (xvi) N,N'-diphenylformamidine, (
xvii) pivaramidine (i.e. 2,2-dimethylpropaneamidine or 2,2-
dimethylpropanimidamide, CAS 18202-73-8), (xviii) 3-pyridine-3-carboximidamide, and (xix) cyclopropylamidine. . Carboxamidine is (i
) DBU or (ii) DBN.

Aspect 7. A moisture-curable polyolefin formulation according to any one of aspects 1-4, wherein the (aza)carboxamidine is an unsubstituted or substituted guanidine. Guanidine can be a compound of formula (II) R ⁶ R ⁷ NC(=NR ⁵ )-NR ⁸ R ⁹ (II), where R ⁵ -R ⁹ are the limits (r1) - (r5): (r1) each of R ⁵ -R ⁹ is independently H or a (C ₁ -C ₄₅ ) hydrocarbyl group; (r2) any two of R ⁵ -R ⁹ bound together to form a (C ₁ -C ₄₅ ) hydrocarbylene, and each of the remaining R ⁵ -R ⁹ is independently H or a (C ₁ -C ₄₅ ) hydrocarbyl group, (r3)R ⁵ ~
Any three of R ⁹ are joined together to form a trivalent (C ₁ -C ₄₅ ) hydrocarbon triradical group, and each of the remaining R ⁵ -R ⁹ is independently H or (C ₁ -C ₄₅ ) hydrocarbyl group, any four of (r4) R ⁵ to R ⁹ joined together to form a tetravalent (C ₁ -C ₄₅
) to form a hydrocarbon tetraradical group and the remaining one of R ⁵ to R ⁹ is H or (C ₁ -C _4
5 ) is a hydrocarbyl group; and (r5) all of R ⁵ -R ⁹ are joined together to form a pentavalent (C ₁ -C ₄₅ ) hydrocarbon pentaradical group. It is as it should be. Guanidines are sometimes referred to as azacarboxamidines because they have an aza nitrogen atom attached to the carbon atom of the carboxamidino group. For example, the aza nitrogen atom of formula (II) is the N attached to ^R8 and ^R9 . Guanidine may be free of NH groups. When the (aza)carboxamidine is guanidine, the moisture-curable polyolefin formulation may be free of carboxamidine.

Aspect 8. Guanidine is (i)-(viii): (i) 1,5,7-triazabicyclo[4.4.0]dec-5-ene (“TBD”), 7-methyl-1,5,7- triazabicyclo[4.4.0]dec-5-ene, (iii) 1,1,3,3-tetramethylguanidine (“TMG”, CAS 80-70-6), (iv) 1,1,2 ,3,3-pentamethylguanidine (“PMG”), (v) 2-tert-butyl-1,1,3,3-tetramethylguanidine (“tBTMG”), (vi) 1,8-bis(tetra methylguanidino)naphthalene, (vii) 1-aminopyrazole, and (viii) 1H-pyrazole-1
- a carboxamide.
Guanidines may include (iii) TMG, (iv) PMG, or (v) tBTMG.

Aspect 9. Additives (C)-(L): (C) organic peroxide, (D) scorch retardant, (E
) antioxidants, (F) tree retarders (water tree and/or electrical tree retarders), (G
(H) a moisture scavenger, (I) a hindered amine light stabilizer (HALS), (J) a processing aid, (K) a moisture generator, and (L) any of (C) to (K) The moisture-curable polyolefin formulation of any one of aspects 1-8, further comprising at least one additive selected from a combination of two or more. The combination of (L) can be any two, or any three, or each of (D), (E), (F), and (I).

Aspect 10. A method of making a moisture-curable polyolefin formulation comprising mixing components including (A) a (hydrolyzable silyl group)-functional polyolefin prepolymer and (B) a condensation cure catalyst system to form (A) and (B); and melting or extruding the mixture to make the moisture-curable polyolefin formulation of any one of aspects 1-9. If (B) is made in situ, (A) is melted and then (A)
to the melt of Co, Zn(alkyl) acetylacetonate first and then (aza
) Add carboxamidine to make a moisture-curable polyolefin formulation where (B) is made in situ. When (B) is prepared in advance, first (aza) carboxamidine and Co
, Zn(alkyl)acetylacetonate and (B) were preformed by mixing together (A
) are melted and then (B) previously prepared is added to the melt of (A) to form a moisture-curable polyolefin formulation. The moisture-curable polyolefin formulation so made can be extruded, pelletized, and/or molded to obtain the moisture-curable polyolefin formulation as a solid (e.g., molded or pelletized). The manufacturing method is (A)
, (B), and at least one additive selected from additives (C) to (L), and mixing at least one of (A), (B), and (C) to (L) Obtaining a mixture containing one and melting or extruding the mixture to obtain (A), (B), and (C)-(L)
) and creating formulation embodiments comprising at least one additive of ). Instead of adding (C) by mixing, the additive (C) organic peroxide is compounded after the melting or extrusion step involving any of (A), (B), and (D)-(K). to obtain a formulation further comprising the soaked (C) organic peroxide.

Aspect 11. made by moisture curing the moisture-curable polyolefin formulation of any one of aspects 1-9, or the moisture-curable polyolefin formulation made by the method of aspect 10, to obtain a moisture-cured polyolefin product; A moisture cured polyolefin product. Moisture-curable polyolefin formulations can be moisture-cured in their solid or molten state.

Aspect 12. An article of manufacture comprising a molded form of the moisture-curable polyolefin blend of any one of aspects 1-9 or the moisture-curable polyolefin product of aspect 11. As an example, the substrate,
There are films, layers of laminates, and coatings on pipes.

Aspect 13. A coated conductor comprising an electrically conductive core and a polymeric layer at least partially surrounding the electrically conductive core, wherein at least a portion of the polymeric layer comprises the moisture cured polyolefin product of aspect 11. The entire polymer layer may comprise a moisture cured polyolefin product. The conductive core may be linear (eg, wire-like) and have a length and proximal and distal ends spaced from each other by the length of the linear shape, and the polymer layer is ,
It can completely surround the conductive core except at the proximal and distal ends. Coated conductors are
It may further include one or more additional polymer layers (which may or may not independently include a moisture cured polyolefin product), and/or an outer shield layer (e.g., a metal sheath or sleeve). .

Aspect 14. 14. A method of conducting electricity, comprising applying a voltage across the conductive core of the coated conductor of aspect 13 to generate a flow of electricity through the conductive core. The conductive core may have a length and a proximal end and a distal end separated by the length, wherein electricity is applied along the length of the conductive core from the proximal end to the distal end or vice versa. can flow to

Aspect 15. A condensation cure catalyst system of 1.5:1 to 2.4:1 (e.g., 2.0:1
. DBU and C with a DBU/Co(II)((alkyl)acac) ₂ molar ratio of 0)
o(II)((alkyl)acac) ₂ mixtures, 1:1 to 2:1 (e.g. 1.0:
a mixture of DBU and Co(III)((alkyl)acac) ₃ with a DBU/Co(III)((alkyl)acac) ₃ molar ratio of 1.0 or 2.0:1.0);1. 5
: 1 to 2.4:1 (e.g. 2.3:1.0) TMG/Zn(II)((alkyl)a
a mixture of TMG and Zn(II)((alkyl)acac) ₂ with a molar ratio of cac) ₂ , 0.19:1 to 10:1 (e.g. 0.19:1.0, 1.7:1 .0, 5.0:1
. 0, or a mixture of DBU and Zn(II)((alkyl)acac) ₂ with a DBU/Zn(II)((alkyl)acac) ₂ molar ratio of 10.0:1.0);
5:1 to 2.4:1 (eg 2:1) DBN/Zn(II)((alkyl)acac
) from the group consisting of mixtures of DBN and Zn(II)((alkyl)acac) ₂ having a molar ratio of ₂ , wherein DBN is 1,5-diazabicyclo[4.3.0]non-5-ene and DBU is 1,8-diazabicyclo[5.4.0]undec-7-ene, TM
G is tetramethylguanidine and each (alkyl)acac is independently unsubstituted acetylacetonate with 1-5 unsubstituted (C ₁ -C ₆ )alkyl groups or (C ₁ -C
₆ ) Condensation cure catalyst systems that are alkyl-substituted acetylacetonates. Either one of the mixtures can be made in situ in (A) (hydrolyzable silyl group)-functional polyolefin prepolymer or (A) (hydrolyzable silyl group)-functional polyolefin prepolymer may be prefabricated separately from and prior to being combined. The mixture can be a mixture used in any one of the examples of the invention described below. each (alkyl) of embodiment 15
acac is unsubstituted acetylacetonate or methyl-substituted acetylacetonate, or methyl-substituted acetylacetonate that is 3-methyl-acetylacetonate or 1,1,5,5-tetramethyl-acetylacetonate, or unsubstituted acetyl It can be acetonate. The (B) condensation cure catalyst system of any one of aspects 1-14 can be the condensation cure catalyst system of aspect 15.

A moisture-curable polyolefin composition. The total weight of all components in the moisture-curable polyolefin formulation is 100.00% by weight. Moisture-curable polyolefin formulations may be free of water (anhydrous) or may additionally contain water.

Moisture-curable polyolefin compositions may be one-part or multi-part formulations, such as
It can be a two-part formulation. A two-part formulation can comprise first and second parts, the first part from (A) a (hydrolyzable silyl group)-functional polyolefin prepolymer and (B) a condensation cure catalyst system. consisting essentially of (A) the additional portion and optionally any one or more of components (C)-(L).

Moisture-curable polyolefin formulations can be in continuous (monolithic) or segmented solid form. A moisture-curable polyolefin formulation may comprise granules and/or pellets. The (A) (hydrolyzable silyl group)-functional polyolefin prepolymer is also prepared in a divided solid form (e.g., granules or pellets) prior to the mixing step used to prepare the moisture-curable polyolefin formulation. ).

Moisture-curable polyolefin formulations are prepared by combining (A) a (hydrolyzable silyl group)-functional polyolefin prepolymer with (B) a catalyst masterbatch comprising a dispersion of a condensation cure catalyst system in a carrier resin, It can be made by taking an embodiment of a moisture-curable polyolefin formulation comprising A), (B), and a carrier resin. The carrier resin of (B) may be an additional amount of (A), or polyethylene homopolymer, ethylene/alpha-olefin copolymer, ethylene/acrylate copolymer, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density It can be a silicon-free ethylene-based polymer such as polyethylene (MDPE), or high density polyethylene (HDPE). The concentration of (B) in the catalyst masterbatch can be up to 20 times the target concentration of (B) in the moisture-curable polyolefin formulation. The catalyst masterbatch can be an embodiment of a moisture-curable polyolefin formulation having an amount (B) greater than 3 wt%. Moisture curable with various lower concentrations of (B) using catalyst masterbatches by combining amounts of base polymer that are the same or different additional amounts of (A) with varying amounts of catalyst masterbatch Other embodiments of polyolefin blends can be made economically.

A moisture-curable polyolefin formulation may consist essentially of components (A) and (B). This expression means that this embodiment of the moisture-curable polyolefin formulation comprises component (i)
(x): (i) unsubstituted or substituted imidazole, (ii) unsubstituted or substituted polyester, (iii) unsubstituted or substituted polyether, (iv) unsubstituted or substituted urea, (v)
tin, (vi) amine-carboxylate, (vii) amine (e.g. triethylamine)
and ammonium compounds ( _{e.g., triethylammonium chloride having the formula HN(CH2CH3)3Cl ) ,} (viii) metal carboxylates (where the metal is calcium,
any metal other than cobalt or zinc, or a metal other than cobalt or zinc), (ix) any seven of (i) to (viii), and (x) (i) to (
viii), each of which may be free of added components selected from any one of. For example, moisture-curable polyolefin formulations contain tin,
Alternatively, it may further include dibutyltin dilaurate, excluding any one, or any six, or each of (i)-(iv), (vi), (vii), and (viii). Alternatively, the moisture-curable polyolefin formulation is tin-free and contains any one, or any six, or (i)-(iv), (vi), (vii), and (v
iii) may not be included. "Additional component" means a component that is intentionally introduced. Some of components (i)-(x) are similar to components previously described (e.g., component (A
) to (L)) as impurities or may be carried over from its synthesis (e.g., (A) or an olefin polymerization catalyst carried over from the synthesis of the carrier resin), whereby the moisture-curable polyolefin Inadvertently introduced into the formulation. These impurities are not expected to have any measurable beneficial or detrimental impact on the performance of moisture-curable polyolefin formulations. Moisture-curable polyolefin products, articles of manufacture, and coated conductors made therefrom, when the moisture-curable polyolefin formulation does not contain any of components (i)-(x), and also methods of making or using them In addition, the same constituents (i) to (x
) may not be included. Embodiments of moisture-curable polyolefin formulations that consist essentially of components (A) and (B) may further contain one or more of any components not explicitly excluded above. Examples of such one or more components not excluded above are optional additives (C)-(L).

Moisture-curable polyolefin formulations may be composed of components (A), (B), and optionally zero, one, or more additives (C)-(L). This embodiment of the moisture-curable polyolefin formulation excludes components not explicitly included.

If an embodiment of a moisture-curable polyolefin formulation does not contain a given component, neither an article containing it or made from it nor a moisture-curable polyolefin product made from it does. , articles containing or made from it, nor methods of making or using it and methods of using it.

The moisture-curable polyolefin formulation is either Co,Zn(alkyl)acetylacetonate-free (aza)carboxamidine or (aza)carboxamidine-free Co,Zn(alkyl)acetylacetonate in place of (B). can be characterized by improved scorch resistance compared to comparative moisture-curable polyolefin formulations containing The scorch resistance is evaluated by the scorch time test method using a moving die rheometer (MDR) described later, and (K) -1 calcium oxalate monohydrate (K) moisture generator is also 1.5% by weight.
as measured by an embodiment of a moisture-curable polyolefin formulation comprising: In some embodiments, the moisture-curable polyolefin formulation has a (aza)carboxamidine/Co,Zn(alkyl)acetylacetonate molar ratio of 15:0.15, alternatively 11:0.18, alternatively 10.4: It can be characterized by improved scorch resistance when it is 0.18, alternatively 10.0:0.19, alternatively 11:5.1.

An embodiment of the moisture-curable polyolefin formulation is Co,Zn(alkyl)acetylacetonate-free (aza)carboxamidine or (aza)carboxamidine-free Co,Zn(alkyl)acetylacetonate in place of (B) Moisture-curing into embodiments of moisture-cured polyolefin products characterized by improved thermal creep resistance compared to comparative moisture-cured polyolefin products made from comparative moisture-cured polyolefin formulations containing either Such embodiments of the moisture-curable polyolefin formulation, and the moisture-curable polyolefin products made therefrom, do not (K) contain (lack) a moisture generating agent. An embodiment of a moisture cured polyolefin product for thermal creep testing is made by the tape extrusion and cure method described below. The thermal creep resistance of such embodiments of moisture cured polyolefin products is measured by the Thermal Creep Test Method described below. Embodiments of moisture-curable polyolefin blends used to make moisture-curable polyolefin products with improved thermal creep resistance are 5:0.5, alternatively 4
. 00:0.9, alternatively 3.00:0.95, alternatively 2.40:0.95, alternatively 2.40:1.6, alternatively 2.30:0.99, alternatively 1.74:1.01 (aza)carboxamidine/Co,Zn(alkyl)acetylacetonate molar ratio of

Moisture curable polyolefin formulations have properties (i)-(v): (i) 50% to 17% after 20 minutes at 200° C. as an average of three specimens measured according to the Thermal Creep Test Method;
4%, alternatively 50% to 150%, alternatively 51% to 120%, alternatively 55% to 94%
(ii) a T of 8.1-15.9 minutes measured according to the T90 cross-linking test method
90 curing time, (iii) the maximum torque (MH) minus the minimum torque (ML) as measured according to the moisture cure test method using a moving die rheometer (MDR) (MH-ML) is 1 .65 to 4.44 deciNewton meters (dN*m), alternatively 1.70 to 4.30 dN*m, alternatively 1.71 to 4.10 dN*m, alternatively 2.2
characterized by any one of (iv) any two of properties (i)-(iii) and (v) each of properties (i)-(iii), which is 0 to 4.10 dN*m obtain. A test method will be described later.

Moisture curable polyolefin formulations consist of components (A) and (B) and 0, 1
, or more optional components.

Component (A) (hydrolyzable silyl group)-functional polyolefin prepolymer ("(
A) Prepolymers"). A polyolefin molecule containing covalently bonded condensation-curable silicon-containing groups. In this case, the polyolefin molecules are further polymerized via water-based condensation curing to form covalently bonded siloxysilyl bridges between different chains of the polyolefin molecules, thereby
More than one structural unit can contribute to at least one type of chain of the resulting moisture-cured polymer product comprising siloxysilyl bridges (Si—O—Si) attached to carbon atoms of different chains. can. . The polyolefin portion of the (A) prepolymer may be polyethylene-based, meaning that the (A) prepolymer has a backbone formed by the polymerization of ethylene. Alternatively, (A) the prepolymer is poly(ethylene-co-(C ₃ -
C ₄₀ ) alpha-olefin) system, which means that the (A) prepolymer has a backbone formed by copolymerization of ethylene and at least one alpha-olefin.

(A) The prepolymer can be a reactor copolymer of ethylene and an alkenyl-functional hydrolyzable silane. Alkenyl-functional hydrolyzable silanes have the formula (III) (R ²
) _m (R ³ ) _3-m Si—(C ₂ -C ₆ )alkenyl (III), wherein
m, R ² and R ³ are as defined above for formula (II). ( _C2 - _C6 )
Alkenyl can be vinyl, allyl, 3-butenyl, or 5-hexenyl. (A
) prepolymer can be a reactor copolymer of ethylene and vinyltrimethoxysilane. Vinyltrimethoxysilane is an example of an alkenyl-functional hydrolyzable silane of formula (III), where subscript m is 3 and each R ² is (C ₁ -C ₆ )alkoxy (i.e. , methoxy) and (C ₂ -C ₆ )alkenyl is vinyl (—C(H)=CH ₂ )
is.

Alternatively, (A) the prepolymer can be a reactor copolymer of ethylene, an alpha-olefin and an alkenyl-functional hydrolyzable silane such as US Pat. No. 6,936,671.

Alternatively, (A) the prepolymer is typically treated with a hydrolyzable unsaturated silane (e.g., vinyltrimethoxysilane) in a post-polymerization formulation or extrusion step promoted by a free radical initiator such as a dialkyl peroxide. ) and isolating the resulting silane-grafted polymer (e.g., S
It can be a homopolymer of ethylene having a carbon atom backbone with hydrolyzable silyl groups grafted thereto, such as polymers made by the IOPLAS™ process). The grafted polymer may be for use in subsequent processing steps. SI
The OPLAS™ process is described, for example, in US 3,646,155 and WO2019/
005439A1. The MONOSIL™ process is described, for example, in the US
2016/0200843A1 and WO2019/005439A1.

Alternatively, the (A) prepolymer is a copolymer of ethylene with one or more of ( _C3 - _C40 ) alpha-olefins and unsaturated carboxylic acid esters (e.g., (meth)acrylate alkyl esters) well, in which case the copolymer is SIOP
It has a backbone with hydrolyzable silyl groups grafted thereto, such as made by the LAS™ process.

Alternatively, (A) the prepolymer is typically treated with a hydrolyzable unsaturated silane (e.g., vinyltrimethoxy silane) and using the resulting silane-grafted polymer immediately (without isolation) in subsequent manufacturing steps (e.g., the MONOSIL™ process). can be a mixture of ethylene, a hydrolyzable silane, such as an alkenyl-functional hydrolyzable silane of formula (III), and a peroxide suitable for use in:

Alternatively, (A) the prepolymer is SIOPLAS™ or MONOSIL (
Copolymers of ethylene with one or more of (C ₃ -C ₄₀ ) alpha-olefins and unsaturated carboxylic acid esters and alkenyl-functional hydrolysis of formula (III) suitable for use in the Trademark process. It can be a mixture of a hydrolyzable silane, such as a hydrolyzable silane, and a peroxide. Alpha-olefins are (C ₃ -C ₄₀ ) alpha-olefins, or (C
₃ -C ₂₀ ) alpha-olefins, or (C ₃ -C ₁₀ ) alpha-olefins. Alpha-olefins can have at least 4 carbon atoms (i.e.
(C ₄ ) alpha-olefins or higher). Examples of (C ₃ -C ₁₀ )alpha-olefins are propylene, 1-butene, 1-hexene, 1-octene, and 1-decene. The peroxide can be an organic peroxide as described in WO2015/149634A1, page 5, line 6 to page 6, line 2, or as described below for (C1) organic peroxides.

Alternatively, (A) (hydrolyzable silyl group)-functional polyolefin prepolymer ((
A) prepolymer) is (i) a reactor copolymer of ethylene and a hydrolyzable silane, (i
i) reactor copolymers of ethylene, hydrolyzable silanes, and one or more alpha-olefins and unsaturated carboxylic acid esters (eg US Pat. No. 6,936,671), (iii)
) a homopolymer of ethylene having a carbon backbone and a hydrolyzable silane grafted onto the carbon backbone (e.g., made by the SILOPAS™ process); (iv) ethylene and one or more having a backbone; with a hydrolyzable silane grafted to its backbone (e.g., SILOP
AS™ process), (v) a copolymer formed from a mixture of ethylene, a hydrolyzable silane, and an organic peroxide (e.g., made by the MONOSIL™ process), or (vi) copolymers formed from mixtures of ethylene, one or more alpha-olefins and unsaturated carboxylic acid esters, hydrolyzable silanes, and organic peroxides (e.g., made by the MONOSIL™ process; ).

(A) prepolymer is 79.0 to 99.99% by weight, alternatively 85.0 to 99.9
9% by weight, alternatively 90.0 to 99.99% by weight, alternatively 95.0 to 99.99% by weight
may be present in the moisture-curable polyolefin formulation at a concentration of When the moisture-curable polyolefin formulation further comprises at least one additive, the maximum amount of (A) is 99.89% by weight, alternatively 99.0% by weight, based on the total weight of the moisture-curable polyolefin formulation. can be

Component (B) Condensation Cure Catalyst System (B) Condensation Cure Catalyst System comprises (aza)carboxamidine to Co, Co, Zn(alkyl)acetylacetonate in a molar ratio of (aza)carboxamidine/Co,Zn(alkyl)acetylacetonate of 15:0.15, respectively. Includes mixtures made by contact with Zn(alkyl)acetylacetonate. (B) Alternatively, the moisture-curable polyolefin formulation may not contain any organic anions that are not (alkyl)acetylacetonate or (aza)carboxamidine anions.

(B) Condensation cure catalyst system is 15:0.15 (aza)carboxamidine/Co,Zn
Characterized by the molar ratio of (alkyl)acetylacetonate. The molar ratio is equal to the number of moles of (aza)carboxamidine used divided by the number of moles of Co,Zn(alkyl)acetylacetonate used. The range from 15 to 0.15 can also be written as 10:1 to 0.15:1 or 10/1 to 0.15/1. (Aza) carboxamidine/Co, Zn
(Alkyl)acetylacetonate molar ratio is 11:0.18, alternatively 10.4:0
. 18, alternatively 10.0:0.19, alternatively 11:5.1, alternatively 4.00:0.
9, alternatively 3.00:0.95, alternatively 2.40:0.95, alternatively 2.40:1
. 6, alternatively 2.30:0.99, alternatively 1.74:1.01.

(B) a mixture of condensation cure catalyst systems comprising (B1) (aza)carboxamidine and Co, Zn
(Alkyl)acetylacetonate, or (B2) the reaction product of the reaction of (aza)carboxamidine with Co, Zn(alkyl)acetylacetonate, or (B3) the reaction product of (B2) and (aza ) carboxamidine and/or Co, Zn (
alkyl) acetylacetonate.

(B1) The blend may comprise a blend of carboxamidine and a cobalt(alkyl)acetylacetonate coordination complex, or a blend of carboxamidine and a zinc(alkyl)acetylacetonate coordination complex. (B1) A blend of guanidine and cobalt (
Alkyl)acetylacetonate coordination complexes, or a blend of guanidine and zinc(alkyl)acetylacetonate coordination complexes.

(B2) The reaction product is a reaction product of a reaction between carboxamidine and a cobalt(alkyl)acetylacetonate coordination complex, or a reaction product of a reaction between carboxamidine and a zinc(alkyl)acetylacetonate coordination complex. can contain. (B2) the reaction product is
It can include the reaction product of the reaction of guanidine with a cobalt(alkyl)acetylacetonate coordination complex, or the reaction product of the reaction of guanidine with a zinc(alkyl)acetylacetonate coordination complex.

(B2) In the preparation of the reaction product, the reaction between (aza)carboxamidine and Co,Zn(alkyl)acetylacetonate can be a proton exchange (acid-base) reaction. Alternatively, the reaction is a ligand exchange reaction in which the neutral oxygen atom of the (alkyl)acetylacetonate of the related coordination complex is replaced with (aza)carboxamidine to create a first hybrid coordination complex of Co or Zn. and the first hybrid coordination complex contains at least one monodentate (alkyl)acetylacetonate ligand (anion) and at least one (aza)carboxamidine. Alternatively, the reaction may be to add a (aza)carboxamidine to a related coordination complex to create a second hybrid coordination complex of Co or Zn, the second hybrid coordination complex being the second Unlike the first hybrid coordination complex, the second hybrid coordination complex comprises two bidentate (alkyl)acetylacetonate ligands and at least one (aza)carboxamidine ligand. Alternatively, the reaction is a combination of any two or more such reactions.

(B2) the reaction product may comprise a metal-ligand complex of formula M(L) _x (Q) _y ;
wherein M is a metal cation selected from Co(II), Co(III), and Zn(II); subscript x is an integer of 2 or 3 and the formal oxidation state of the metal cation each group L is independently an anionic ligand that is (alkyl)acetylacetonate, carboxamidine anion, or guanidine anion; each group Q is independently acetylacetone, carboxamidine, or a neutral ligand that is guanidine;
The subscript y is 0-3; at least one group L is a carboxamidine or guanidine anion, or at least one group Q is a carboxamidine or guanidine.

(B2) The reaction product may be pre-made separately (if not present) from (A) (hydrolyzable silyl group)-functional polyolefin prepolymer. For example, (B2) preforms (B2) the reaction product separately from (A) by contacting carboxamidine or guanidine with Co,Zn(alkyl)acetylacetonate in an aprotic solvent, and then A previously prepared (B2) reaction product may be combined with (A) (hydrolyzable silyl group)-functional polyolefin prepolymer to form a moisture-curable polyolefin formulation.
Optionally, the aprotic solvent can be removed from the preformed (B2) reaction product after the contacting step and before the combining step. Removal can be by distillation, evaporation, freeze-drying, or stripping. The preformed (B2) reaction product used in the combining step may be anhydrous and optionally free of aprotic solvents.

Alternatively, the (B2) reaction product can be made in situ in the presence of (A) (hydrolyzable silyl group)-functional polyolefin prepolymer. For example, (B2) can be prepared by sequentially combining (A) (hydrolyzable silyl groups)-functional polyolefin prepolymers with (A) (hydrolyzable silyl groups)-functional polyolefin prepolymers, (aza)carboxamidines or Co,Zn(alkyl)acetylacetonates, but not both. can be made in situ to make either a combination of (aza)carboxamidine and (A), or a combination of Co,Zn(alkyl)acetylacetonate and (A), and then combine the combination with (aza) In situ (B
2) the reaction product can be made in situ;

(B2) Combination of reaction product with (B3) of (aza)carboxamidine and/or Co,Zn(alkyl)acetylacetonate. (B3) The combination is (Aza)
It can be made when carboxamidine and Co,Zn(alkyl)acetylacetonate are mixed in non-stoichiometric proportions. (B3) is the (B2) reaction product and excess (aza)
It can be in combination with carboxamidine and does not contain Co,Zn(alkyl)acetylacetonate. (B3) The combination can be the combination of the (B2) reaction product with an excess of Co,Zn(alkyl)acetylacetonate and does not contain (aza)carboxamidine. (B3) is (B2) the reaction product, (B1) (aza)carboxamidine and Co, Z
It can be in combination with blends with n(alkyl)acetylacetonates.

(B) The (aza)carboxamidines of formula (I) or (II) of the condensation cure catalyst system embodiments have the limits (i)-(x): (i) R ¹ -R ⁴ or R ⁵ -R ⁹ at least one, or each, is a (C ₁ -C ₄₅ )alkyl group; (ii) R ¹ -R ⁴ or R ⁵ -R ⁹
is a (C ₂ -C ₄₅ )alkenyl group; (iii)
) at least one, or one or two of R ¹ to R ⁴ or R ⁵ to R ⁹ are (C ₆ -C
₁₂ ) is an aryl group; (iv) at least one, or one or two of R ¹ to R ⁴ or R ⁵ to R ⁹ are (C ₁ -C ₂₅ )alkyl-substituted (C ₆ -C ₁₂ )aryl groups; (v) at least one, or one or two of R ¹ to R ⁴ or R ⁵ to R ⁹ are (C
₆ -C ₁₂ ) is an aryl-substituted (C ₁ -C ₂₅ )alkyl group; (vi) at least one or each of R ¹ -R ⁴ or R ⁵ -R ⁹ is an unsubstituted linear (C _{1 -C 25} )alkyl group; (vii) any two of R ¹ to R ⁴ or any two _of R ⁵ to R ⁹ are joined together to form a (C ₁ -C ₅ ) alkylene group; , at least one of the remaining R ¹ -R ⁴ or R ⁵ -R ⁹ is independently as defined in any one of (i)-(vi); (viii) R ¹ -R any three of ⁴ or any three of R ⁵ to R ⁹ are joined together to form a trivalent (C ₄ -C ₁₀ )alkane triradical group and the remaining R ¹ to R ⁴ or R ⁵ at least one of to R ⁹ is independently as defined in any one of (i) to (vi); (ix) each of R ^{1 to} R and (x) each of R ⁵ -R ⁹ are joined together to form a valent (C ₄ -C ₁₂ )alkanetetraradical group of 5
forming a valent (C ₅ -C ₁₄ )alkane pentaradical group.

(B) the condensation cure catalyst system may be characterized as being substantially pure before it is combined with the (A) prepolymer. "Substantially pure" (B) is 90 to 1 of the total weight of (B)
00 wt%, alternatively 95-100 wt%, alternatively 98-100 wt%, alternatively 90
, 95, or 98 to 99.99% by weight.

(B) The (aza)carboxamidine used in the condensation cure catalyst system has a neutral (free base)
form, or a protonic acid salt form containing a protonic acid.

(B) The Co, Zn(alkyl) acetylacetonate used in the condensation cure catalyst system can be in anhydrous form (not including hydrates) or in hydrated form. Co, Zn in anhydrous form
(Alkyl)acetylacetonates can beneficially help minimize scorch in moisture-curable polyolefin formulations. Scorch is premature moisture curing of a moisture-curable polyolefin formulation during its extrusion (eg, in an extruder). The hydrated form of Co,Zn(alkyl)acetylacetonate can further beneficially serve as an in-situ source of water molecules for moisture-curing moisture-curable polyolefin formulations in anhydrous or low relative humidity environments. The balance between minimizing scorch and allowing in-situ moisture cure is achieved by adding Co, Zn(alkyl)acetylacetonate and (D) a water scorch retardant in moisture-curable polyolefin formulations. It can be achieved by using a hydrated form.

(B) The amount of condensation cure catalyst system is equal to the sum of the amount of (aza)carboxamidine and the amount of Co,Zn(alkyl)acetylacetonate used to make their mixture. The amount of (B) is from 11.0 to 3.1 wt%, alternatively from 3.0 to 0.05 wt%, alternatively from 1.0 to 0.10 wt% (eg, 0. 15% by weight)
can be

Optional Component (C) Peroxides: containing carbon atoms, hydrogen atoms, and two or more oxygen atoms and having at least one —O—O— group, provided that two or more — OO-
A molecule or molecules provided that, when groups are present, each -O-O- group is indirectly bonded to another -O-O- group through one or more carbon atoms Aggregate of. (C) peroxide comprises heating a moisture-curable polyolefin formulation comprising components (A), (B), and (C) to a temperature above the decomposition temperature of (C) peroxide It can be added to moisture-curable polyolefin formulations for curing.

(C) Peroxides can be (C1) hydrocarbyl hydroperoxides. (C1
) can be a compound of the formula R ^O —O—O—H, where R ^O is independently (C ₁ -C ₂₀ )
It is an alkyl group or a (C ₆ -C ₂₀ )aryl group. Each (C ₁ -C ₂₀ )alkyl group is independently unsubstituted or substituted with one or two (C ₆ -C ₁₂ )aryl groups. Each (C ₆ -C ₂₀ )aryl group is unsubstituted or has 1 to 4 (C
₁ - _C10 ) substituted with an alkyl group. (C1) Hydroperoxide can be 1,1-dimethylethyl hydroperoxide, 1,1-dimethylpropyl hydroperoxide, benzoyl hydroperoxide, tert-butyl hydroperoxide, tert-amyl hydroperoxide, or cumyl hydroperoxide. Cumyl hydroperoxide can be isopropyl cumyl hydroperoxide, t-butyl cumyl hydroperoxide, or cumyl hydroperoxide, or cumene hydroperoxide (cumene hydroperoxide, alpha, alpha-dimethylbenzyl hydroperoxide, CAS numbers 80-15). -9).

(C) The peroxide can be (C2) an organic peroxide. (C2) is represented by the formula R ^O —O—O
—R 2 ^O monoperoxide, where each R 2 ^O is independently as defined above. Alternatively, (C2) can be a diperoxide of the formula R ^O —O—O—R ^a —O—O—R ^O , where R ^a is (C ₂ -C ₁₀ )alkylene, (C ₃ —C ₁₀ )cycloalkylene,
or a divalent hydrocarbon group such as phenylene, where each R 2 ^O is independently as defined above. (C2) organic peroxides include bis(1,1-dimethylethyl) peroxide, bis(
1,1-dimethylpropyl) peroxide, 2,5-dimethyl-2,5-bis(1,1-
dimethylethylperoxy)hexane, 2,5-dimethyl-2,5-bis(1,1-dimethylethylperoxy)hexyne, 4,4-bis(1,1-dimethylethylperoxy)
Valeric acid, butyl ester, 1,1-bis(1,1-dimethylethylperoxy)-3,3
,5-trimethylcyclohexane, benzoyl peroxide, tert-butyl peroxybenzoate, di-tert-amyl peroxide (“DTAP”), bis(alpha-t-butyl-peroxyisopropyl)benzene (“BIPB”), isopropylcumyl t-butyl peroxide, t-butyl cumyl peroxide, di-t-butyl peroxide, 2,5
-bis(t-butylperoxy)-2,5-dimethylhexane, 2,5-bis(t-butylperoxy)-2,5-dimethylhexyne-3,1,1-bis(t-butylperoxy)- 3,3,5-trimethylcyclohexane, isopropylcumylmilperoxide,
It can be 4,4-di(tert-butylperoxy)butyl valerate, or di(isopropylcumyl)peroxide, or dicumylperoxide. The organic peroxide can be dicumyl peroxide.

A blend of two or more different (C) peroxides can be used.

At least one or each (C) peroxide may contain one -O-O- group.

The moisture-curable polyolefin formulation may be (C) free of peroxides. (C) Peroxide, if present, from 0.01 to 4.5% by weight of the formulation of the present invention, alternatively 0.05
It can be ~2 wt%, alternatively 0.2-0.8 wt%.

Without being bound by theory, (C) the use of peroxides allows for a dual cure mechanism, resulting in moisture-cured polyolefin products that are products of moisture curing and free-radical curing of moisture-curable polyolefin formulations. It is believed that embodiments are obtained. Moisture curing can form crosslinks between the hydrolyzable silane groups of (A), where the crosslinks are C—Si—O—
It has a Si—C bond motif. (C) Peroxide-enabled free radical curing can form carbon-carbon bond crosslinks between the polymer chains of (A). Thus, the dual-cure product has a higher cross-link content than the moisture-cure-only product and thus improved mechanical properties (e.g., modulus, thermal creep performance).

optional components (additives) (D) scorch retarders: molecules that inhibit premature curing;
Or an assembly of such molecules. Examples of scorch retarders are hindered phenols, semi-hindered phenols, TEMPO, TEMPO derivatives, 1,1-diphenylethylene, 2
,4-diphenyl-4-methyl-1-pentene (also called alpha-methylstyrene dimer or AMSD), and allyl-containing compounds described in US6277925B1, column 2, line 62 to column 3, line 46. . The polyolefin composition and crosslinked polyolefin product may be free of (D). (D) A scorch retardant, if present, from 0.01 to 1.5% of the scorch retardant, all based on the total weight of the formulations and/or products of the present invention.
It can be 5 wt%, alternatively 0.1-1.0 wt%.

Optional Components (Additives) (E) Antioxidants: Organic molecules or aggregates of such molecules that inhibit oxidation. (E) Antioxidants function to provide antioxidant properties to moisture-curable polyolefin formulations and/or crosslinked polyolefin products. Examples of suitable (E) are bis(4-(1-methyl-1-phenylethyl)phenyl)amine (eg NAUGARD445), 2,2′-methylene-bis(4-methyl-6-t-butylphenol ) (e.g. VANOX MBPC), 2,2′-thiobis(2-t-butyl-5-methylphenol (CAS No. 90-66-4, 4,4′-thiobis(2-t-butyl-5-methyl phenol) (4,4′-thiobis (also known as 6-tert-butyl-m-cresol), CAS number 96-69-5, commercially available LOWINOX TB
M-6), 2,2′-thiobis(6-t-butyl-4-methylphenol (CAS No. 9
0-66-4, commercially available LOWINOX TBP-6), tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazine-2
,4,6-trione (e.g. CYANOX1790), pentaerythritol tetrakis (3-(3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl)propionate) (e.g. IRGANOX1010, CAS No. 6683-19) -8), 3,
5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid 2,2′-thiodiethanediyl ester (for example, IRGANOX1035, CAS No. 41484-
35-9), distearyl thiodipropionate (“DSTDP”), dilauryl thiodipropionate (eg IRGANOX PS800), stearyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate. (for example, IRGANOX10
76), 2,4-bis(dodecylthiomethyl)-6-methylphenyl (IRGANOX1
726), 4,6-bis(octylthiomethyl)-o-cresol (eg IRGAN
OX1520), and 2′,3-bis[[3-[3,5-di-tert-butyl-4-
Hydroxyphenyl]propionyl]]propionohydrazide (IRGANOX1024
). (E) is 4,4′-thiobis(2-t-butyl-5-methylphenol) (
4,4′-thiobis(6-tert-butyl-m-cresol)),
2,2′-thiobis(6-t-butyl-4-methylphenol, tris[(4-tert
-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazine-2,4,6-trione, distearyl thiodipropionate, or dilauryl thiodipropionate, or can be a combination of any two or more of The combination was tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazine-2,4,6-trione and distearylthiodipropionate. may The moisture-curable polyolefin formulation and/or crosslinked polyolefin product may be free of (E). (E) Antioxidants, if present, constitute 0.0 of the total weight of the moisture-curable polyolefin formulation and/or crosslinked polyolefin product.
01 to 1.5 wt%, alternatively 0.1 to 1.0 wt%.

Optional Component (F) Tree Retarders: Molecules or aggregates of such molecules that inhibit water and/or electrical trees. The tree retarder can be a water tree retarder or an electrical tree retarder. A water tree retardant is a compound that inhibits water tree, a process by which polyolefins degrade when exposed to the combined effects of an electric field and humidity or moisture. An electrical tree retarder is a compound that inhibits electrical tree, an electrical pre-decomposition process in solid electrical insulation by partial discharge. Electric trees can occur in the absence of water. Water trees and electrical trees are a problem for electrical cables containing coated conductors, where the coating contains polyolefins. (F) can be poly(ethylene glycol) (PEG). The polyolefin composition and crosslinked polyolefin product may be free of (F). (F) a tree retardant, based on the total weight of the formulation of the present invention, from 0.01 to 1
. It can be 5 wt%, alternatively 0.1-1.0 wt%.

Optional Components (Additives) (G) Colorants. For example, pigments or dyes. for example,
carbon black or titanium dioxide. Carbon black is a poly(1-butene-co-ethylene) copolymer (≧95 wt % to less than 100 wt % of the total weight of the masterbatch)
, and carbon black (greater than 0% to ≦5% by weight of the total weight of the masterbatch).
It is a microcrystalline form of paracrystalline carbon with a high surface area to volume ratio, but lower than that of activated carbon.
Examples of carbon black are furnace carbon black, acetylene carbon black,
Conductive carbons such as carbon fibers, carbon nanotubes, graphene, graphite, and expanded graphite platelets. The moisture-curable polyolefin formulation and/or crosslinked polyolefin product may be free of (G). (G), if present, can be from 0.1 to 35%, alternatively from 1 to 10% by weight of the formulation of the invention.

Optional Components (Additives) (H) Moisture Scavengers. (H) Moisture scavengers function to inhibit premature moisture cure of moisture-curable polyolefin formulations, where premature moisture cure results in premature or prolonged exposure of the moisture-curable polyolefin formulation to ambient air. arises from being Examples of (H) are octyltriethoxysilane and octyltrimethoxysilane. The moisture-curable polyolefin formulation and/or crosslinked polyolefin product may be free of (H). (H) is 0.001 of the formulation of the present invention, if present
~0.2 wt%, alternatively 0.01-0.10 wt%.

Optional Components (Additives) (I) Hindered Amine Light Stabilizers: Molecules containing a basic nitrogen atom bound to at least one sterically bulky organic group and functioning as inhibitors of degradation or decomposition; Or an assembly of such molecules. (I) is a compound that has a sterically hindered amino functional group, inhibits oxidative degradation, and can also increase the shelf life of embodiments of the polyolefin composition containing (C) an organic peroxide. be. Examples of suitable (I) are butanedioic acid dimethyl ester, 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine-ethanol (CAS number 65447-77-0, commercially available LOWILITE 62)
and N,N'-bisformyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-hexamethylenediamine (CAS No. 124172-
53-8, commercially available Uvinul 4050 H). The formulations and products of the invention may be free of (I). (I) hindered amine stabilizers, if present, from 0.001 to 1.5%, alternatively from 0.002 to 1.0%, alternatively 0% by weight of the formulations of the present invention;
. 05-1.0% by weight.

Optional Components (Additives) (J) Processing Aids: Molecules that reduce polymer melt sticking in manufacturing equipment such as extruders and dies and reduce melt fracture of materials. (J) can be fluoropolymers, polyorganosiloxanes, metal salts of fatty carboxylic acids, fatty carboxamides, waxes, ethylene oxide (co)polymers, and nonionic surfactants. The formulations and products of the invention may be free of (J). (J) Processing aids, if present, may be from 0.05 to 5% by weight of the formulation of the present invention.

Optional Components (Additives) (K) Moisture Generating Agents: (a) hydrate molecules that release water molecules when heated, or (b) decompose to produce water molecules (as a by-product) when heated Molecules of potential water sources. (K) (a) can be a hydrate form of a Group 1 or Group 2 metal oxalate, such as calcium oxalate monohydrate. (K)(b) can be a mixture of a sulfonic acid and a peroxide, which mixture evolves water when heated. The formulations and products of the invention may be free of (K). (K) Moisture generating agents, if present, may be from 0.5 to 2.5%, alternatively from 1.0 to 1.9% by weight of the formulations of the present invention.

The formulations and/or products of the present invention may contain lubricants, mineral oils, antiblocking agents, metal deactivators (e.g., oxalylbis(benzylidene)hydrazide (OABH)), auxiliary agents, nucleating agents, or flame retardants. It can contain more.

Any optional component can be useful in imparting at least one characteristic or property to formulations and/or products of the invention in need thereof. A feature or property can be useful in improving the performance of the inventive formulations and/or products in operations or applications in which the inventive formulations and/or products are exposed to elevated operating temperatures.
Such operations or applications include melt compounding, extrusion, molding, hot water pipes, and insulating layers for power cables.
Chemical substance

Any compound herein includes naturally occurring and/or isotopically enriched forms,
Including all isotopic forms thereof. Isotopically enriched forms may have additional uses, such as medical or anti-counterfeiting applications.

Any compound, chemical composition, formulation, material, or product herein may be H, Li
, Be, B, C, N, O, F, Na, Mg, Al, Si, P, S, Cl, K, Ca, Sc
, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, B
r, Rb, Sr, Y, Zn, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In,
Sn, Sb, Te, I, Cs, Ba, Hf, Ta, W, Re, Os, Ir, Pt, Au,
Any one of the chemical elements selected from the group consisting of Hg, Tl, Pb, Bi, lanthanides, and actinides may be absent, provided that the chemical elements necessary for them (for example, C and H) are not excluded.

Each (C ₁ -C ₄₅ )hydrocarbyl group is independently a (C ₁ -C ₄₅ )alkyl group,
(C ₂ -C ₄₅ )alkenyl group, (C ₆ -C ₁₂ )aryl group, (C ₁ -C ₂₅ )alkyl-substituted (C ₆ -C ₁₂ )aryl group, or (C ₆ -C ₁₂ )aryl-substituted ( _C1 - _C2
5 ) can be an alkyl group;

Each (C ₁ -C ₄₅ )hydrocarbylene group is independently a (C ₁ -C ₄₅ )alkylene group, (C ₂ -C ₄₅ )alkenylene group, (C ₆ -C ₁₂ )arylene group, (C ₁ - _C25
) alkyl substituted (C ₆ -C ₁₂ ) arylene group, or (C ₆ -C ₁₂ ) aryl substituted (
C ₁ -C ₂₅ ) alkylene group.

Each trivalent, tetravalent, and pentavalent (C ₁ -C ₄₅ ) hydrocarbon is each independently (C
₁ - _C45 ) alkane, ( _C2 - _C45 ) alkene, ( _C6 - _C12 ) arene, ( _C1
—C ₂₅ )alkyl-substituted (C ₆ -C ₁₂ )arenes, or trivalent, tetravalent, or pentavalent derivatives of (C ₆ -C ₁₂ )aryl-substituted (C ₁ -C ₂₅ )alkanes.

each (C ₁ -C ₄₅ ) hydrocarbyl group, (C ₁ -C ₄₅ ) hydrocarbylene, trivalent (C ₁ -C ₄₅ ) hydrocarbon, tetravalent (C ₁ -C ₄₅ ) hydrocarbon, and 5 (C ₁ -C
₄₅ ) Hydrocarbons are independently unsubstituted or halogen, unsubstituted (C ₁ -C ₆
) alkyl, —NH ₂ , —N(H) (unsubstituted (C ₁ -C ₆ )alkyl), —N (unsubstituted (
substituted with 1 to 5 substituents independently selected from C ₁ -C ₆ )alkyl) ₂ , —OH, and —O(unsubstituted (C ₁ -C ₆ )alkyl).

Substitution means that one or more carbon-bonded hydrogen atoms (H atoms of C—H) are formally replaced by the same number of independently selected substituents (one substituent per H atom of C—H) means substituted to form one or more carbon-bonded substituents up to and including one substitution;
all H atoms of C-H are replaced by substituents;

"Unsubstituted" means that atoms consist of carbon and hydrogen atoms.

Unsubstituted (C ₁ -C ₆ )alkyl is independently straight chain, branched chain, or cyclic (unsubstituted (
unsubstituted (C ₁ -C ₆ )alkyl which is C ₃ -C ₆ )alkyl).

An unsubstituted ( _C3 )alkyl group is a monovalent radical (monoradical) of _the formula _C3H7 . Examples are -CH ₂ CH ₂ CH ₃ and -CH(CH ₃ ) ₂ . _An unsubstituted ( _C4 )alkyl group is a monoradical of formula _C4H9 . Examples are -CH ₂ CH ₂ CH ₂ CH ₃ , -CH(
CH ₃ )CH ₂ CH ₃ , —C(CH ₃ ) ₂ CH ₃ , —CH ₂ CH(CH ₃ )CH ₃ , and —C(CH ₃ ) ₃ . _An unsubstituted ( _C5 )alkyl group is a monoradical of formula _C5H11 . Examples are -CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ , -CH(CH ₃ )CH ₂ CH ₂ CH ₃
, —C(CH ₃ ) ₂ CH ₂ CH ₃ , —CH ₂ CH(CH ₃ )CH ₂ CH ₃ , —CH ₂ C(
_CH3 ) _{2CH3 , -CH2CH2CH ( CH3} ) _CH3 , -CH( _CH2CH3 ) _{2 ,}
and —CH ₂ C(CH ₃ ) ₃ . An unsubstituted ( _C6 )alkyl group is a monoradical of _the formula _C6H13 . Examples are -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ , -CH(CH ₃ )C
_{H2CH2CH2CH3 , -C ( CH3 ) 2CH2CH2CH3 , -CH2CH ( CH3}
)CH ₂ CH ₂ CH ₃ , —CH ₂ C(CH ₃ ) ₂ CH ₂ CH ₃ , —CH ₂ CH ₂ CH(C
_H3 ) _{CH2CH3 , -CH2CH2C} ( _CH3 ) _2CH3 , _-C ( _CH3 ) _{( CH2C}
H ₃ ) ₂ , and —CH ₂ CH ₂ C(CH ₃ ) ₃ .

(Alkyl) acetylacetonate: monoanionic derivative (conjugate base) of unsubstituted or alkyl-substituted acetylacetone. Unsubstituted acetylacetone has the formula CH ₃ C(=O)CH
₂ C(=O) _CH3 , including enol isomers of the formula _CH3C (=O)CHC(OH) _CH3 . Unsubstituted acetylacetonate has the formula CH ₃ C(=O)CH=C(O-)
Drawn as the enolate of _CH3 , it is formally prepared by mono-deprotonating unsubstituted acetylacetone. Alkyl-substituted acetylacetone is formally derived from unsubstituted acetylacetone by replacing at least a carbon-bonded H atom with an alkyl group such as Ra as defined above. Alkyl-substituted acetylacetonates are formally made by monodeprotonating alkyl-substituted acetylacetones.

Carboxamide: A compound with a pentavalent functional group of formula CC(=O)-N, where the functional group is not part of a heteroaromatic ring. Also known as an amide.

Carboxamidine: a compound having a hexavalent functional group of the formula NC(=N-)-C,
Functional groups are not part of the heteroaromatic ring. Also known as amidine.

Guanidine: A compound with a pentavalent functional group of the formula NC(=N-)-N, where the functional group is not part of a heteroaromatic ring.

Organic anion: a negatively charged ion of a hydrocarbon or heterohydrocarbon. A negative charge (density) may reside on one or more atoms independently selected from carbon, nitrogen, oxygen, and sulfur. For example, in 1-methylethoxide (the anion of 2-propanol) the negative charge resides on the oxygen atom. In unsubstituted acetylacetone (the anion of unsubstituted acetylacetone),
The negative charge resides partially on the two oxygen atoms and partially on the C-3 carbon atom.

Protic acid: independently HCl, HBr, HI, acetic acid, or methanesulfonic acid.
definition

Alternatively, it precedes a different embodiment.

Ambient or room temperature: 23°C ± 1°C unless otherwise stated.

Aspect: an embodiment of the invention. "Some aspects" etc. modify numbered and unnumbered aspects.

ASTM: Standard Organization, ASTM International (West Cons
Hohocken, Pennsylvania, USA).

The comparative examples are used for comparison and should not be considered prior art.

Free or absent means completely absent or undetectable.

IEC: Standards Organization, International Electrotechnical Commission, Geneva, Switzerland.

IUPAC stands for International Union of Pure and Applied Chemistry (IUPAC Secretariat (R
Search Triangle Park, North Carolina, USA
)).

Masterbatch: A concentrated mixture of additives dispersed in a carrier resin.

may is not required and gives permission for choice.

The generalized format "metal (roman numerals)" (e.g., "cobalt (II)"
or "Co(III)"), the Roman numeral (eg, (II) or (III)) indicates the formal oxidation state (eg, +2 or +3) of the metal (eg, cobalt or Co).

Effective: Functionally possible or effective.

Optional (optionally): absent (or excluded) or present (or included).

PPM or parts per million: weight basis unless otherwise stated.

Properties: Measured using standard test methods and their known conditions unless otherwise specified.

Ranges include endpoints, subranges, and integer and/or fractional values subsumed therein, provided that a range of integers does not include fractional values.

Density: Measured according to ASTM D792-13, Standard Test Method for Density and Specific Gravity (Relative Density) of Plastics by Displacement, Method B (for testing solid plastics in liquids other than water, e.g. liquid 2-propanol). be. Unit of gram of one cubic centimeter (g/cm ³ ).

Melt Index "I ₂ ": 190°C/2.0°C, formerly known as "Condition E".
Measured according to ASTM D1238-13 using 16 kg conditions. Units of grams per 10 minutes (g/10 minutes).

Carboxamidine compound: 1,8-diazabicyclo[5.4.0]undeca-7-
ene (DBU) and 1,5-diazabicyclo[4.3.0]non-5-ene (DBN)
. Obtained from TCI Shanghai, China.

A guanzidine compound: tetramethylguanidine (TMG). TCI Shanghai
Obtained from i, China.

Co,Zn(alkyl)acetylacetonate compound: Co(II)(acac) ₂
, Co(III)(acac) ₃ , and Zn(II)(acac) ₂ . Each acac is 2
, 4-pentanedionate. Obtained from TCI Shanghai, China.

High Density Polyethylene 1 (HDPE1): A high density polyethylene homopolymer with a density of 0.965 g/cm ³ and a melt index (I ₂ ) of 8 g/10 min.

(Hydrolyzable silyl groups)-functional prepolymer (A)-1: Reactor copolymer of 98.5 wt% ethylene and 1.5 wt% vinyltrimethoxysilane. It was prepared by copolymerizing ethylene and vinyltrimethoxysilane in a tubular high pressure polyethylene reactor using a free radical initiator. The Dow Chemical Compa
Available as SI-LINK™ DFDA-5451 from ny.

Condensation curing catalyst system (B)-1: molar ratio of DBU/Co(II)(acac) ₂ is 2.0
: in-situ-made mixture of DBU and Co(II)(acac) ₂ , which is 1.0.

Condensation curing catalyst system (B)-2: the molar ratio of TMG/Zn(II)(acac) ₂ is 2.3
: an in-situ-made mixture of TMG and Zn(II)(acac) ₂ , which is 1.0.

Condensation curing catalyst system (B)-3: molar ratio of DBU/Zn(II)(acac) ₂ is 1.7
: 1.0 for an in situ prepared mixture of DBU and Zn(II)(acac) ₂ .

Condensation curing catalyst system (B)-4: molar ratio of DBN/Zn(II)(acac) ₂ is 2.1
: an in-situ-made mixture of DBN and Zn(II)(acac) ₂ , which is 1.0.

Condensation curing catalyst system (B)-5: molar ratio of DBU/Zn(II)(acac) ₂ is 1:1
, a pre-made mixture of DBU and Zn(II)(acac) ₂ . Zn in it
(II) To a measured volume of anhydrous tetrahydrofuran (THF) sufficient to make a 0.1 molar solution of (acac) is added a measured amount of DBU and Zn(II)(acac).
) is pre-made by dissolving ₂ . The solution is heated at 60° C. for 3 hours. Volatiles (THF) are removed under reduced pressure to give (B)-5.

Condensation curing catalyst system (B)-6: molar ratio of DBU/Zn(II)(acac) ₂ is 2:1
, a pre-made mixture of DBU and Zn(II)(acac) ₂ . Zn(II)
Pre-made according to the method used to pre-make (B)-5, except using twice as much DBU compared to (acac) ₂ .

Condensation curing catalyst system (B)-7: molar ratio of DBU/Zn(II)(acac) ₂ is 1.7
: an in-situ-made mixture of DBU and Zn(II)(acac) ₂ , which is 1.0.

Condensation curing catalyst system (B)-8: molar ratio of DBU/Zn(II)(acac) ₂ is 2:1
, an in situ prepared mixture of DBU and Zn(II)(acac) ₂ .

Condensation curing catalyst system (B)-9: molar ratio of DBU/Co(II)(acac) ₂ is 2.0
: in-situ-made mixture of DBU and Co(II)(acac) ₂ , which is 1.0.

Condensation curing catalyst system (B)-10: molar ratio of DBU/Co(III)(acac) ₃ is 1
: 1, an in situ prepared mixture of DBU and Co(III)(acac) ₃ .

Condensation curing catalyst system (B)-11: molar ratio of DBU/Co(III)(acac) ₃ is 2
. In situ prepared mixture of DBU and Co(III)(acac) ₃ , 0:1.0.

Condensation curing catalyst system (B)-12: molar ratio of DBU/Zn(II)(acac) ₂ is 5.
In situ prepared mixture of DBU and Zn(II)(acac) ₂ , 0:1.0.

Condensation curing catalyst system (B)-13: molar ratio of DBU/Zn(II)(acac) ₂ is 0.
In situ prepared mixture of DBU and Zn(II)(acac) ₂ , 19:1.0.

Condensation curing catalyst system (B)-14: molar ratio of DBU/Zn(II)(acac) ₂ is 10
. In situ prepared mixture of DBU and Zn(II)(acac) ₂ , 0:1.0.

Comparative Condensation Cure Catalyst System (B)-15: In Situ DBU and Zn(II)(acac) ₂ with a DBU/Zn(II)(acac) ₂ molar ratio of 0.10:1.0 Mixtures made (comparison for molar ratio).

Each acac of (B)-1 through (B)-15 is an unsubstituted acetylacetonate (ie, 2,4-pentanedionate).

Antioxidant (E)-1: pentaerythritol tetrakis (3-(3,5-bis(1
,1-dimethylethyl)-4-hydroxyphenyl)propionate (eg IRGA
NOX 1010, CAS No. 6683-19-8; BASF)

Antioxidant (E)-2: 2',3-bis[[3-[3,5-di-tert-butyl-
4-Hydroxyphenyl]propionyl]]propionohydrazide (IRGANOX 1
024; BASF).

Moisture generating agent (K)-1: calcium oxalate monohydrate. Used as a water source for curing experiments performed using a moving die rheometer (MDR) instrument.
Part A: Formulations Containing (K)-1 Moisture Generating Agents

Moisture Curable Polyolefin Formulation Method 1: HAAKE Mixer (Thermo
Fisher Scientific), (A) (hydrolyzable silyl group)-functionalized polyolefin prepolymer (eg ((A)-1) at 120° C. and 0 revolutions per minute (rp
m) for 5 minutes, then 120° C. and 45 rpm for 2.5 minutes. To the fully melted (A), (B) the condensation cure catalyst system is quickly added. For example, first Co(II)(ac
ac) Addition of ₂ followed by addition of DBU to make (B)-1 in situ, first with Zn(II
)(acac) ₂ and then TMG to make (B)-2 in situ, first Z
addition of n(II)(acac) ₂ followed by DBU to make (B)-3 in situ;
First add Zn(II)(acac) ₂ and then add DBN to make (B)-4 in situ, add pre-made (B)-5, or pre-made (B) Add -6. The contents are mixed for 1 minute at 120° C. and 45 rpm. If necessary, (K) moisture generator (eg, (K)-1) is added in small portions, then mixing is continued for 2 minutes at 120° C. and 45 rpm. Remove the material from the mixer and press the sample to form a plaque according to the Plaque Preparation Test Method.

Plaque Preparation Test Method: A sample of the material from Moisture Curable Polyolefin Formulation Method 1 was pressed at 120°C and 0.5 megapascals (MPa) for 20 seconds to form a plaque, measuring 1-4 millimeters (mm ) thick plaque. The thickness of the plaque can vary, inter alia, depending on the degree of scorching of the formulation during its preparation (eg, in the HAAKE mixer).

Moisture Cure Test Method Using a Moving Die Rheometer (MDR): A 4.5 gram sample of the material from Moisture Curable Polyolefin Formulation Method 1 was measured using ASTM
Cure at 180° C. according to D5289-17 (Standard Test Method for Rubber Physical Vulcanization Using a Rotorless Cure Meter). Using plaques prepared by the plaque preparation test method, MDR and minimum torque (ML) at 180° C. are measured using the following procedure. Moving die rheometer (MDR) equipment MDR2000 (Alpha Technolo
gies) while heating the test sample at 180° C. for 20 minutes while monitoring the torque change of 0.5 arc degrees of oscillatory deformation at 100 cycles per minute (cpm; 1.67 hertz (Hz)). The lowest torque value measured is denoted as "ML" in deciNewton meters (dN*m).
shown as ML indicates the degree of pre-curing of the formulation during the plaque preparation test method, MDR
is the starting point for the moisture cure of the present invention using As the moisture curing (crosslinking) of the present invention progresses,
The measured torque value increases and finally reaches the maximum torque value. The maximum or highest measured torque value is indicated as "MH" expressed in dN*m. All other things being equal, the higher the MH torque value, the greater the degree of cross-linking. All other things being equal, the faster the torque value from ML to 1 lb/inch (1.1 dN*m), the faster the cure rate of the test sample. Conversely, the longer the time required to go from the torque value ML to 1 lb/inch (1.1 dN*m), the slower the cure speed of the test sample. ML indicates the rheological change of the curing process, with higher values indicating a higher degree of cross-linking. ML=1.0 lbf. in (1.
Record the cure time required to reach 1 deciNewton meter). 1.00 lb/i
n=0.113 Newton meters (N*m).

Scorch time test method. This method characterizes the scorch resistance of moisture-curable polyolefin formulations prepared as pellets. Resistance to scorch is the length of time it takes to increase the torque by 1 pound inch (lb/in) above the minimum torque (ML) measured at 180°C using the Moisture Curing Test Method using the MDR. ts
1 (1.0 lb/in = 1.1 dN*m). 1.00 lb/in = 0.113 Newton meters (Nm). A longer ts1 time advantageously results in a greater degree of scorch resistance (also known as scorch retardancy). Moisture curable polyolefin formulations are 180
It can be characterized by its resistance to scorch at °C. (MDR ts1) Measured according to the 8-16 minute scorch time test method. In order for a sample to be said to exhibit scorch resistance according to this MDRts1 method, the measured maximum torque (MH) value must be at least 1.0 dN*m higher than the measured minimum torque (ML) value ( That is, MH-ML ≥ 1.0dN
*m). A sample is characterized as having no scorch resistance if MH-ML<1.0 dN*m.

T90 cross-linking time test method. This method characterizes the cure rate as the length of time required to reach 90% cross-linking (T90) in minutes. The T90 curing time is 9 times from the minimum torque ML to the maximum torque MH measured at 180°C using the moisture cure test method using MDR.
It is the length of time it takes to increase the torque to 0% (0.90MH).

Comparative Examples 1-5 (CE1-CE5): Comparative formulations were prepared using moisture generator (K)-1 and tested according to the methods described above. See the results listed in Table 1 below.

Inventive Examples 1-10 (IE1-IE10): Inventive moisture curable polyolefin formulations were prepared using moisture generator (K)-1 and tested according to the methods described above. See the results set forth in Tables 2 and 3 below.

As shown in Table 1, the comparative formulations exhibited poor cure as indicated by the substantially lower maximum torque values MH. As shown in Tables 2 and 3, the formulations of the present invention produced cured products with a significant degree of cross-linking as indicated by the substantially higher maximum torque values MH. In addition, the formulations of the present invention generally had faster cure rates and therefore produced cured products in less time, as indicated by the shorter T90 cross-linking times.
Part B: (K) Formulation without (lack of) moisture generator.

Preparation of catalyst masterbatches 1-5 (invention). HDPE1 is added into a Brabender mixer (Brabender GmbH & Co KG) at 160° C. and 10 rpm until completely melted. Add antioxidants (E)-1 and (E)-2 to the melt. Then (B) the condensation cure catalyst system is added. For example, first add Zn(II)(acac) ₂ and then add DBU to make (B)-7 in situ, first add Zn(II)(acac)
₂ is added followed by DBU to make (B)-8 in situ, first Co(II)(a
cac) ₂ is added followed by DBU to make (B)-9 in situ, first with Co(I
II) (acac) ₂ is added followed by DBU to make (B)-10 or (B)-11 respectively in situ. Alternatively (prophetically), add premade (B)-5 or add premade (B)-6 to make a catalyst masterbatch from a premade condensation cure catalyst system. The resulting formulation is mixed for 2 minutes at 155° C. and 45 rpm. Remove the mixture from the mixer and hot press the sample into a plaque using the Plaque Preparation Test Method. Cut the plaque into small pellets. The pellets are fed to a short screw extruder to make small pellets of moisture curable polyolefin formulation as catalyst masterbatches 1, 2, 3, 4, or 5, respectively. Catalyst Masterbatches 1-5 are 3.33 wt% Antioxidant (E)-1 and 1.67 wt% Antioxidant (E)-2, and 2
. 6 wt% (B) condensation cure catalyst system (B)-7, (B)-8, (B)-9, (B)-10
, or (B)-11, respectively.

Comparative Masterbatches 1-4 were each prepared by the same procedure as that for preparing Catalyst Masterbatch 1, but instead of 2.6 wt% of the (B)-7 condensation cure catalyst system, Comparative Masterbatches 1-4 , the following constituents Zn(II)(acac) ₂ , DBU, Co(II) (
acac) ₂ , and a different one of Co(III)(acac) ₃ each
. It contained 3% by weight.

Tape Extrusion and Curing Method: Measured amounts of Catalyst Masterbatch 1 (see Preparation of Catalyst Masterbatch 1) and (Hydrolyzable Silyl Groups)-functionalized prepolymer at weight/weight ratios of 5.8/94.2 respectively. (A)-1 is dry blended in a vinyl bag. The dry blend is then fed to a single screw extruder operating at 160° C. and 45 rpm to extrude the moisture curable polyolefin blend as a 1 mm thick tape with a width of about 3.5 mm. The formulation does not contain (K) a moisture generating agent. A "dogbone" shaped specimen is then cut from the extruded tape and cured by immersion in a 90° C. water bath for 3 hours to produce an example of the moisture cured polyolefin product of the present invention. The thermal creep of moisture cured polyolefin products is measured according to the Thermal Creep Test Method.

Thermal creep test method. The degree of cross-linking, and thus the degree of curing, is measured in test samples of moisture-cured polyolefin products prepared by the tape extrusion and curing method. 20 Newtons per square centimeter (N/c
m ² ) and cured (3 hours in a water bath at 90° C.) test sample ((K
) containing no moisture generating agent) is subjected to thermal creep. After 20 minutes the final length is measured. Cool and measure the length of the tested sample. Dividing the amount of elongation by the initial length provides a measure of thermal creep as a percentage. The degree of elongation of the test specimen is expressed as a percentage (%) of the length of the test specimen after the thermal creep condition relative to the initial length of the test specimen before the thermal creep condition.
The lower the thermal creep percentage, the lower the degree of elongation under load of the test specimen, which in turn increases the degree of cross-linking, which in turn increases the degree of curing. A lower thermal creep value suggests a higher degree of cross-linking.

Comparative Examples 6-9 (CE6-CE9): The comparative formulations are each Comparative Masterbatch 1
4, containing no moisture generator (K), and tested according to the method described above. See the results listed in Table 4 below.

Inventive Examples 11-15 (IE11-IE15): Moisture-curable polyolefin formulations of the present invention were prepared from a different one of Catalyst Masterbatches 1-5, respectively,
It contained no moisture generator (K) and was tested according to the method described above. See the results set forth in Table 5 below.

As shown in Table 4, the comparative formulations were considered to have minimal or no cross-linking, as indicated by fracture of all specimens in less than 1 minute (elongation at break very long), A cured product could therefore not be obtained. As shown in Table 5, the formulations of the present invention are:
All specimens remained intact after 20 minutes at 200°C with thermal creep values of substantially 100
%, resulting in cured products of the invention having substantially greater cross-linking. The lower the thermal creep %, the greater the degree of cross-linking, and the greater the degree of cross-linking, the more suitable the moisture cured polyolefin product is for use as a power cable jacket.

As shown in Table 4, the comparative formulations were considered to have minimal or no cross-linking, as indicated by fracture of all specimens in less than 1 minute (elongation at break very long), A cured product could therefore not be obtained. As shown in Table 5, the formulations of the present invention performed well, as indicated by the fact that all test specimens remained intact after 20 minutes at 200° C. and had thermal creep values substantially less than 100%. resulted in cured products of the present invention having substantially greater cross-linking. The lower the thermal creep %, the greater the degree of cross-linking, and the greater the degree of cross-linking, the more suitable the moisture cured polyolefin product is for use as a power cable jacket.
The present invention includes the following aspects.
Section 1.
A moisture-curable polyolefin formulation comprising:
(A) (hydrolyzable silyl group)-functional polyolefin prepolymer;
(B) a carboxamidine or guanidine, unsubstituted or substituted compound (collectively referred to as "(aza)carboxamidine") is a cobalt acetylacetonate coordination complex or a zinc acetylacetonate coordination complex; A compound in which each acetylacetonate is independently unsubstituted or substituted with 1 to 5 alkyl groups, each alkyl group being unsubstituted ("Co,Zn(alkyl)acetylacetonate and a condensation cure catalyst system comprising a mixture made by contacting Co,Zn(alkyl)acetylacetonate with cobalt (II) ((alkyl)acetylacetonate). phosphate) ₂ , cobalt (III) ((alkyl)acetylacetonate) ₃ , and zinc (II) ((alkyl)acetylacetonate) ₂ ;
wherein the amount of (A) is from 79.0 to 99.99 weight percent (wt %) and the amount of (B) is from 21.0 to 0.01 wt. % and
A moisture-curable polyolefin formulation wherein said (B) condensation cure catalyst system is characterized by a (aza)carboxamidine/Co,Zn(alkyl)acetylacetonate molar ratio of 15:0.15.
Section 2.
The (A) (hydrolyzable silyl group)-functional polyolefin prepolymer has the following limitations (i) to (iii): (i) each hydrolyzable silyl group independently has the formula (R ² ) _m (R ³ ) _3-m Si— monovalent group, where subscript m is an integer of 1, 2, or 3, and each R ² is independently H, HO—, (C ₁ -C ₆ )alkoxy, (C ₂ -C ₆ )carboxy, phenoxy, (C ₁ -C ₆ )alkyl-phenoxy, ((C ₁ -C ₆ )alkyl) ₂ N-, (C ₁ -C ₆ ) _{( _ _} ^_ _{_ _} ii) the polyolefin portion of (A) is based on polyethylene, poly(ethylene-co-(C ₃ -C ₄₀ ) alpha-olefin), or combinations thereof; and (iii) (i) and (ii) 2. The moisture-curable polyolefin blend of paragraph 1, characterized by any one of:
Item 3.
The mixture of the (B) condensation curing catalyst system comprises (B1) to (B3): (B1) a blend of the (aza) carboxamidine and the Co, Zn (alkyl) acetylacetonate, (B2) the (aza) (B3) the reaction product of (B2) and the (aza)carboxamidine and/or the Co,Zn(alkyl)acetylacetonate; 3. The moisture-curable polyolefin blend according to paragraph 1 or 2, which is any one of a combination of
Section 4.
of paragraphs 1 to 3, wherein each (alkyl)acetylacetonate of said Co,Zn(alkyl)acetylacetonate is independently an unsubstituted acetylacetonate or a (C ₁ -C ₆ )alkyl-substituted acetylacetonate. Moisture-curable polyolefin formulation according to any one of the preceding claims.
Item 5.
Moisture-curable polyolefin formulation according to any one of claims 1 to 4, wherein said (aza)carboxamidine is an unsubstituted or substituted carboxamidine.
Item 6.
(i) to (xix): (i) 1,8-diazabicyclo[5.4.0]undec-7-ene, (ii) 1,5-diazabicyclo[4.3.0]non- 5-ene, (iii) 1,2,4-triazole-1-carboximidamide, (iv) acetamidine, (v) aminoacetamidine, (vi) benzamidine, (vii) 4-amino-benzamidine, (viii) ) 4-bromo-benzamidine, (ix) 4-chlorobenzamidine, (x) 4-fluorobenzamidine, (xi) 4-hydroxybenzamidine, (xii) 4-methoxybenzamidine, (xiii) 4-methylbenz amidine, (xiv) 4-trifluoromethylbenzamidine, (xv) N,N'-formamidine, (xvi) N,N'-diphenylformamidine, (xvii) pivaramidine, (xviii) 3-pyridine-3- 6. The moisture-curable polyolefin blend of paragraph 5, which is any one of carboximidamide and (xix) cyclopropylamidine.
Item 7.
Moisture-curable polyolefin formulation according to any one of claims 1 to 4, wherein said (aza)carboxamidine is an unsubstituted or substituted guanidine.
Item 8.
the guanidine is (i) to (viii): (i) 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Dec-5-ene, (iii) 1,1,3,3-tetramethylguanidine, (iv) 1,1,2,3,3-pentamethylguanidine, (v) 2- tert-butyl-1,1,3,3-tetramethylguanidine, (vi) 1,8-bis(tetramethylguanidino)naphthalene, (vii) 1-aminopyrazole, and (viii) 1H-pyrazole-1-carboxamide 8. The moisture-curable polyolefin blend of paragraph 7, which is any one of
Item 9.
Additives (C)-(L): (C) organic peroxides, (D) scorch retarders, (E) antioxidants, (F) tree retarders (water tree and/or electrical tree retarders), (G) a colorant, (H) a moisture scavenger, (I) a hindered amine light stabilizer, (J) a processing aid, (K) a moisture generator, and (L) any two of (C) to (K) 9. The moisture-curable polyolefin formulation of any one of paragraphs 1-8, further comprising at least one additive selected from a combination of one or more.
Item 10.
A method of making a moisture-curable polyolefin formulation, comprising mixing components including (A) a (hydrolyzable silyl group)-functional polyolefin prepolymer and (B) a condensation cure catalyst system to produce (A ) and (B), and melting or extruding said mixture to make the moisture-curable polyolefin formulation of any one of paragraphs 1-9.
Item 11.
Moisture curing the moisture-curable polyolefin blend of any one of Items 1 to 9 or the moisture-curable polyolefin blend made by the method of Item 10 to obtain a moisture-curable polyolefin product. A moisture cured polyolefin product made by
Item 12.
An article of manufacture comprising a molded form of the moisture-curable polyolefin blend of any one of paragraphs 1-9 or the moisture-curable polyolefin product of paragraph 11.
Item 13.
A coated conductor comprising a conductive core and a polymeric layer at least partially surrounding said conductive core, at least a portion of said polymeric layer comprising the moisture cured polyolefin product of paragraph 11. conductor.
Item 14.
14. A method of conducting electricity, comprising applying a voltage across a conductive core of the coated conductor of paragraph 13 to produce a flow of electricity through said conductive core.
Item 15.
A condensation cure catalyst system comprising:
a mixture of DBU and Co(II)((alkyl)acac) ₂ with a DBU/Co(II)((alkyl)acac) ₂ molar ratio of 1.5:1 to 2.4:1;
a mixture of DBU and Co(III)((alkyl)acac) ₃ with a DBU/Co(III)((alkyl)acac) ₃ molar ratio of 1:1 to 2:1;
a mixture of TMG and Zn(II)((alkyl)acac) ₂ with a TMG/Zn(II)((alkyl)acac) ₂ molar ratio of 1.5:1 to 2.4:1;
mixtures of DBU and Zn(II)((alkyl)acac) ₂ with a DBU/Zn(II)((alkyl)acac) ₂ molar ratio of 0.19:1 to 10:1, and 1.5:1 selected from the group consisting of mixtures of DBN and Zn(II)((alkyl)acac) ₂ having a molar ratio of DBN/Zn(II)((alkyl)acac) ₂ of ˜2.4:1;
DBN is 1,5-diazabicyclo[4.3.0]non-5-ene, DBU is 1,8-diazabicyclo[5.4.0]undec-7-ene, and TMG is 1 , _1,3,3 -tetramethylguanidine, wherein each (alkyl)acac is independently an _{unsubstituted} acetylacetonate or (C ₁ -C ₆ ) A condensation cure catalyst system that is an alkyl-substituted acetylacetonate.

Claims (15)

A moisture-curable polyolefin formulation comprising:
(A) (hydrolyzable silyl group)-functional polyolefin prepolymer;
(B) a carboxamidine or guanidine, unsubstituted or substituted compound (collectively referred to as "(aza)carboxamidine") is a cobalt acetylacetonate coordination complex or a zinc acetylacetonate coordination complex; A compound in which each acetylacetonate is independently unsubstituted or substituted with 1 to 5 alkyl groups, each alkyl group being unsubstituted ("Co,Zn(alkyl)acetylacetonate and a condensation cure catalyst system comprising a mixture made by contacting Co,Zn(alkyl)acetylacetonate with cobalt (II) ((alkyl)acetylacetonate). phosphate) ₂ , cobalt (III) ((alkyl)acetylacetonate) ₃ , and zinc (II) ((alkyl)acetylacetonate) ₂ ;
Each of the moisture-curable polyolefin formulations has an amount of (A) of 79.0
~99.99 weight percent (wt%), the amount of (B) is from 21.0 to 0.01 wt%,
The (B) condensation cure catalyst system is a 15:0.15 (aza)carboxamidine/Co
, Zn(alkyl)acetylacetonate. The (A) (hydrolyzable silyl group)-functional polyolefin prepolymer is restricted (
i) to (iii): (i) each hydrolyzable silyl group is independently of the formula (R ² ) _m (R ³ ) _3-
m is a monovalent group of Si-, where the subscript m is an integer of 1, 2, or 3 and each R ² is independently H, HO-, (C ₁ -C ₆ ) alkoxy, (C ₂ -C ₆ ) carboxy,
phenoxy, (C ₁ -C ₆ )alkyl)-phenoxy, ((C ₁ -C ₆ )alkyl) ₂ N
-, (C ₁ -C ₆ )alkyl(H)C=NO-, or ((C ₁ -C ₆ )alkyl) _2C
=NO- and each R ³ is independently (C ₁ -C ₆ )alkyl or phenyl;
ii) the polyolefin portion of (A) is polyethylene-based, poly(ethylene-co-(C ₃ -
_C40 ) alpha-olefin) systems, or combinations thereof; and (ii)
2. The moisture-curable polyolefin blend of Claim 1, characterized by any one of i) being both (i) and (ii) The mixture of (B) the condensation curing catalyst system comprises (B1) to (B3): (B1) the (Aza)
a blend of carboxamidine and said Co,Zn(alkyl)acetylacetonate, (
B2) the reaction product of the reaction between the (aza)carboxamidine and the Co, Zn (alkyl) acetylacetonate, (B3) the reaction product of (B2) and the (aza) carboxamidine and/or the Co, Zn ( Alkyl) acetylacetonate in combination,
3. A moisture curable polyolefin blend according to claim 1 or 2, which is any one of Claims 1-3, wherein each (alkyl)acetylacetonate of said Co,Zn(alkyl)acetylacetonate is independently unsubstituted acetylacetonate or (C ₁ -C ₆ )alkyl-substituted acetylacetonate. A moisture-curable polyolefin formulation according to any one of Claims 1 to 3. Moisture-curable polyolefin formulation according to any one of the preceding claims, wherein the (aza)carboxamidine is an unsubstituted or substituted carboxamidine. The carboxamidine is (i)-(xix): (i) 1,8-diazabicyclo[5
. 4.0]undec-7-ene, (ii) 1,5-diazabicyclo[4.3.0]non-
5-ene, (iii) 1,2,4-triazole-1-carboximidamide, (iv) acetamidine, (v) aminoacetamidine, (vi) benzamidine, (vii) 4-
amino-benzamidine, (viii) 4-bromo-benzamidine, (ix) 4-chlorobenzamidine, (x) 4-fluorobenzamidine, (xi) 4-hydroxybenzamidine, (xii) 4-methoxybenzamidine, ( xiii) 4-methylbenzamidine, (xiv) 4-trifluoromethylbenzamidine, (xv) N,N'-formamidine, (xvi) N,N'-diphenylformamidine, (xvii) pivaramidine, (xviii) 6. The moisture-curable polyolefin blend of claim 5, which is one of 3-pyridine-3-carboximidamide and (xix) cyclopropylamidine. Moisture-curable polyolefin formulation according to any one of the preceding claims, wherein the (aza)carboxamidine is an unsubstituted or substituted guanidine. The guanidine is selected from (i) to (viii): (i) 1,5,7-triazabicyclo [
4.4.0]dec-5-ene,7-methyl-1,5,7-triazabicyclo[4.4.0
]dec-5-ene, (iii) 1,1,3,3-tetramethylguanidine, (iv) 1,
1,2,3,3-pentamethylguanidine, (v) 2-tert-butyl-1,1,3,
3-tetramethylguanidine, (vi) 1,8-bis(tetramethylguanidino)naphthalene, (vii) 1-aminopyrazole, and (viii) 1H-pyrazole-1-carboxamide. Item 8. A moisture-curable polyolefin blend according to item 7. Additives (C)-(L): (C) organic peroxides, (D) scorch retarders, (E) antioxidants, (F) tree retarders (water tree and/or electrical tree retarders), (G) a colorant, (H) a moisture scavenger, (I) a hindered amine light stabilizer, (J) a processing aid, (K) a moisture generator, and (L) any two of (C) to (K) Moisture-curable polyolefin formulation according to any one of claims 1 to 8, further comprising at least one additive selected from a combination of one or more. A method of making a moisture-curable polyolefin formulation, comprising mixing components including (A) a (hydrolyzable silyl group)-functional polyolefin prepolymer and (B) a condensation cure catalyst system to produce (A ) and (B), and melting or extruding said mixture to make a moisture-curable polyolefin formulation according to any one of claims 1-9. . Moisture curing the moisture curable polyolefin blend of any one of claims 1 to 9, or the moisture curable polyolefin blend made by the method of claim 10, to produce a moisture cured polyolefin product A moisture cured polyolefin product made by obtaining An article of manufacture comprising the moisture-curable polyolefin blend of any one of claims 1-9 or a molded form of the moisture-curable polyolefin product of claim 11. 12. A coated conductor comprising a conductive core and a polymer layer at least partially surrounding said conductive core, at least a portion of said polymer layer comprising the moisture cured polyolefin product of claim 11, covered conductor. 14. A method of conducting electricity, comprising applying a voltage across a conductive core of the covered conductor of claim 13 to generate a flow of electricity through said conductive core. A condensation cure catalyst system comprising:
a mixture of DBU and Co(II)((alkyl)acac) ₂ with a DBU/Co(II)((alkyl)acac) ₂ molar ratio of 1.5:1 to 2.4:1;
a mixture of DBU and Co(III)((alkyl)acac) ₃ with a DBU/Co(III)((alkyl)acac) ₃ molar ratio of 1:1 to 2:1;
a mixture of TMG and Zn(II)((alkyl)acac) ₂ with a TMG/Zn(II)((alkyl)acac) ₂ molar ratio of 1.5:1 to 2.4:1;
mixtures of DBU and Zn(II)((alkyl)acac) ₂ with a DBU/Zn(II)((alkyl)acac) ₂ molar ratio of 0.19:1 to 10:1, and 1.5:1 selected from the group consisting of mixtures of DBN and Zn(II)((alkyl)acac) ₂ having a molar ratio of DBN/Zn(II)((alkyl)acac) ₂ of ˜2.4:1;
DBN is 1,5-diazabicyclo[4.3.0]non-5-ene, DBU is 1,8-diazabicyclo[5.4.0]undec-7-ene, and TMG is 1 , 1
, 3,3-tetramethylguanidine and each (alkyl)acac is independently 1 to
unsubstituted acetylacetonate with 5 unsubstituted (C ₁ -C ₆ )alkyl groups or (C
₁ -C ₆ ) A condensation cure catalyst system that is an alkyl-substituted acetylacetonate.